JP5373231B1 - Laminate with excellent sound insulation - Google Patents

Abstract

の化合物（Ｉ）の含有量ａ１が２０〜６０質量部であり、式（ＩＩ）：
【化２】

の化合物（ＩＩ）の含有量がａ２質量部であるＡ層と、平均残存水酸基量１０〜３５モル％のポリビニルアセタール（Ｂ）１００質量部に対し化合物（Ｉ）の含有量ｂ１が３５〜７５質量部であり、化合物（ＩＩ）の含有量がｂ２質量部であるＢ層との積層体であって、ａ２が０又は（ｂ２／ｂ１）／（ａ２／ａ１）＞１であり、（ｂ１−ａ１）＞０であり、ａ２／ａ１が０〜０．０５であり、ｂ２／ｂ１が０．００１〜０．０８である、積層体。It is a laminate that uses a plasticizer that is compatible with polyvinyl acetal, has excellent plasticizing effect on polyvinyl acetal, and is difficult to extract and volatilize by water, and its sound insulation changes when its moisture content is changed. Provide something that doesn't happen.
Formula (I): 100 parts by mass of polyvinyl acetal (A) having an average residual hydroxyl group content of 25 to 45 mol%:
[Chemical 1]

The content a1 of the compound (I) is 20 to 60 parts by mass, and the formula (II):
[Chemical 2]

The content b1 of the compound (I) is 35 to 75 relative to 100 parts by mass of the A layer in which the content of the compound (II) is a2 parts by mass and the polyvinyl acetal (B) having an average residual hydroxyl group content of 10 to 35 mol%. It is a laminated body with the B layer which is a part by mass and the content of the compound (II) is b2 parts by mass, wherein a2 is 0 or (b2 / b1) / (a2 / a1)> 1 and (b1 -A1)> 0, a2 / a1 is from 0 to 0.05, and b2 / b1 is from 0.001 to 0.08.

Description

  The present invention relates to a laminate containing polyvinyl acetal.

  Sheets containing polyvinyl acetal and a plasticizer are widely used as interlayer films for laminated glass because of their excellent adhesion and transparency to glass and mechanical strength.

  The interlayer film for laminated glass is usually used in a state containing a small amount of water. The moisture content of the interlayer film for laminated glass needs to be appropriately selected depending on the type of the laminated glass manufacturing process. For example, when producing laminated glass on a large scale, due to its high productivity, the glass and the laminated glass interlayer film are temporarily bonded with a nip roll, and then heated and pressurized with an autoclave to perform main bonding. The method is widely used. Since this method does not include a reduced pressure treatment step in a series of steps, the risk of water volatilizing during the production of laminated glass and foaming in the interlayer film for laminated glass is low. Therefore, in this method, the water content of the interlayer film for laminated glass is adjusted to be relatively high (for example, about 0.4 to 0.7%) from the viewpoint of simplifying the humidity control process.

  On the other hand, since an autoclave is expensive, a vacuum bag or a vacuum laminator is used for producing laminated glass, particularly when it is difficult to introduce a large and expensive apparatus. In these methods, a laminated glass is produced by heat-treating a glass and a laminated glass interlayer film under reduced pressure, so there is a risk that water will foam in the laminated glass interlayer film, resulting in bubbles and loss of appearance. high. Therefore, from the viewpoint of improving the yield in the production of laminated glass, usually, the water content of the interlayer film for laminated glass is adjusted to be relatively low (for example, about 0.01 to 0.3%).

  In recent years, interest in sound insulation and soundproofing has been increasing for the purpose of improving the quality of the living environment. In particular, in vehicles such as automobiles, railroads, airplanes, and buildings such as houses and commercial buildings, sound intrusion from window glass becomes a problem, so sound insulating laminated glass using an interlayer film for sound insulating laminated glass is used. More and more cases are used. As an interlayer film for sound insulating laminated glass, a layer with a low plasticizer content for the purpose of manifesting mechanical strength or adhesion to glass and a layer with a high plasticizer content for the expression of sound insulating properties are laminated. The multilayer interlayer film is generally used (see Patent Documents 1 and 2).

  By the way, in the interlayer film for sound insulating laminated glass, it is known that the sound insulating property of the laminated glass using it changes depending on the moisture content (see Patent Document 3). When a laminated glass is manufactured by adjusting the moisture content of the multilayer interlayer film to about 0.01 to 0.3%, the sound insulation is less than when the moisture content is adjusted to 0.4 to 0.7%. descend.

  In addition, the interlayer film for laminated glass generally contains a plasticizer, but the plasticizer is extracted by water adhering to the exposed portion of the interlayer film at the end of the laminated glass, and the glass and the interlayer film are separated. The appearance of the laminated glass may be impaired due to peeling or bubbles. Further, depending on the type of plasticizer, the plasticizer may volatilize from the edge of the laminated glass when a reduced pressure process is performed during the production of the laminated glass or when the laminated glass is used for a long time.

JP 2007-331959 A International Publication No. 2010/038801 International Publication No. 2010/008053

  The present invention solves the above problems, and the plasticizer contained in the laminate is difficult to be extracted by water and hardly volatilized. When used as an interlayer film for laminated glass, sound insulation is achieved even when the moisture content is changed. It aims at providing the laminated body from which a change of property does not occur.

（式中、Ｒ^１およびＲ^２は同一でも異なっていてもよい炭素数７〜１１の炭化水素基を表し、ｍは３〜１０の自然数を表す。）で示される化合物（Ｉ）の含有量ａ１が２０〜６０質量部であり、一般式（ＩＩ）：

（式中、Ｒ^３はＲ^１またはＲ^２のいずれかと同一である。ｎは３〜１０の自然数を表す。）で示される化合物（ＩＩ）の含有量がａ２質量部であるＡ層と、平均残存水酸基量１０〜３５モル％のポリビニルアセタール（Ｂ）１００質量部に対し前記化合物（Ｉ）の含有量ｂ１が３５〜７５質量部であり、前記化合物（ＩＩ）の含有量がｂ２質量部であるＢ層との積層体であって、ａ２が０又は（ｂ２／ｂ１）／（ａ２／ａ１）＞１であり、（ｂ１−ａ１）＞０であり、ａ２／ａ１が０〜０．０５であり、且つｂ２／ｂ１が０．００１〜０．０８である、積層体を提供することで好適に達成される。According to the present invention, the above object is achieved by adding the general formula (I):

(Wherein R ¹ and R ² represent the same or different hydrocarbon groups having 7 to 11 carbon atoms, and m represents a natural number of 3 to 10). Content of Compound (I) a1 is 20 to 60 parts by mass, and the general formula (II):

(Wherein R ³ is the same as either R ¹ or R ² , n represents a natural number of 3 to 10) and the A layer has an a2 mass part content of compound (II); The content b1 of the compound (I) is 35 to 75 parts by mass with respect to 100 parts by mass of the polyvinyl acetal (B) having an average residual hydroxyl group content of 10 to 35 mol%, and the content of the compound (II) is b2 parts by mass. A2 is 0 or (b2 / b1) / (a2 / a1)> 1, (b1-a1)> 0, and a2 / a1 is 0 to 0.00. This is preferably achieved by providing a laminate that is 05 and b2 / b1 is 0.001 to 0.08.

  It is preferable that A layer contains 0.001-0.1 mass part of magnesium salts with respect to 100 mass parts of polyvinyl acetal (A).

  m and n are preferably the same.

R ¹ and R ² are preferably the same.

R ¹ and R ² are preferably a 3-heptyl group.

  It is preferably composed of three or more layers, and both outermost layers are preferably A layers.

  According to the present invention, the above object is preferably achieved by providing a laminated glass including the laminate.

  According to the present invention, the plasticizer contained in the laminate is difficult to be extracted and volatilized by water, and when used as an interlayer film for laminated glass, the laminate does not cause a change in sound insulation even when the moisture content is changed. Can provide the body.

  First, the polyvinyl acetal (A) and the polyvinyl acetal (B) contained in the layer A and the layer B constituting the laminate of the present invention will be described.

  The average residual hydroxyl group content of the polyvinyl acetal (A) is 25 to 45 mol%, preferably 25 to 40 mol%, more preferably 25 to 35 mol%. If the average residual hydroxyl group content is less than 25 mol%, the mechanical strength of the laminate and the adhesion to glass may be reduced. If the average residual hydroxyl group content exceeds 45 mol%, the compound contained in the A layer The compatibility with (I) may be reduced. The degree of acetalization of the polyvinyl acetal (A) is preferably 50 to 74 mol%, more preferably 60 to 74 mol%, and further preferably 65 to 74 mol%. When the degree of acetalization of the polyvinyl acetal (A) is less than 50 mol%, the compatibility with the compound (I) contained in the A layer may be lowered. The strength may be insufficient. The average residual vinyl ester group amount of the polyvinyl acetal (A) is preferably 0.01 to 5 mol%, more preferably 0.01 to 4 mol%, and 0.01 to 3 mol%. More preferably. Polyvinyl acetal having an average residual vinyl ester group content of less than 0.01 mol% is difficult to produce industrially at low cost. When the average residual vinyl ester group amount of the polyvinyl acetal (A) exceeds 5 mol%, the average residual hydroxyl group amount of the polyvinyl acetal (A) is increased by hydrolysis of the vinyl ester group when the laminate is used over a long period of time. The compatibility with compound (I) may change over time.

  The average residual hydroxyl group content of the polyvinyl acetal (B) used in the present invention is 10 to 35 mol%, preferably 13 to 30 mol%, and more preferably 15 to 25 mol%. Polyvinyl acetal having an average residual hydroxyl group content of less than 10 mol% is difficult to produce industrially at low cost. When the average residual vinyl ester group amount of the polyvinyl acetal (B) exceeds 35 mol%, the compatibility with the compound (I) contained in the B layer may be lowered. The degree of acetalization of the polyvinyl acetal (B) is preferably 60 to 85 mol%, more preferably 65 to 82 mol%, and further preferably 69 to 78 mol%. When the degree of acetalization of the polyvinyl acetal (A) is less than 60 mol%, the compatibility with the compound (I) contained in the B layer may be lowered. Polyvinyl acetal having an acetalization degree exceeding 85 mol% is difficult to produce industrially at low cost. The average residual vinyl ester group amount of the polyvinyl acetal (B) is preferably 0.01 to 20 mol%, more preferably 0.5 to 16 mol%, and 4 to 13 mol%. More preferably. Polyvinyl acetal having an average residual vinyl ester group content of less than 0.01 mol% is difficult to produce industrially at low cost. When the average residual vinyl ester group amount exceeds 20 mol%, the average residual hydroxyl group amount of the polyvinyl acetal (B) increases by hydrolysis when used over a long period of time, and the compatibility with the compound (I) increases with time. May change significantly.

  The polyvinyl acetal (A) and the polyvinyl acetal (B) used in the present invention are produced using polyvinyl alcohol as a raw material. Polyvinyl alcohol can be obtained by a conventionally known method. That is, it can be obtained by polymerizing a vinyl ester compound and saponifying the obtained polymer. As a method for polymerizing the vinyl ester compound, conventionally known methods such as a solution polymerization method, a bulk polymerization method, a suspension polymerization method, and an emulsion polymerization method can be applied. As a polymerization initiator used in these polymerization methods, an azo initiator, a peroxide initiator, a redox initiator, or the like can be used as appropriate. The saponification reaction is carried out by subjecting the vinyl ester group of the polymer to alcoholysis or hydrolysis using a conventionally known alkali catalyst or acid catalyst. Among them, the saponification reaction using methanol as a solvent and caustic soda (NaOH) as a catalyst is simple and most preferable.

  Examples of the vinyl ester compound include conventionally known carboxylic acid vinyl esters such as vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl stearate, vinyl benzoate, and vinyl acetate is preferred.

  Also, unless the polyvinyl alcohol is contrary to the gist of the present invention, a modified polyvinyl alcohol obtained by saponifying a copolymer obtained by copolymerizing a vinyl ester compound and a monomer copolymerizable with the vinyl ester compound is used. You can also The monomer copolymerizable with the vinyl ester compound is usually used in a proportion of less than 10 mol% with respect to the vinyl ester compound.

  The viscosity average polymerization degree of polyvinyl alcohol used as a raw material for the polyvinyl acetal used in the present invention is not particularly limited and can be appropriately selected according to the use, but is usually preferably 150 to 3000, more preferably 800 to 2500, and 1000 to 2000. Is more preferable. When the viscosity average polymerization degree of polyvinyl alcohol is lower than 150, the resulting laminate tends to have insufficient mechanical strength, and when it is higher than 3000, the laminate is easy to handle, especially laminated glass for use as an interlayer film for laminated glass. The ease of manufacturing tends to decrease.

  The polyvinyl acetal used in the present invention can be produced by a conventionally known method. For example, it can be produced by a precipitation method under the following reaction conditions. First, a polyvinyl alcohol aqueous solution having a concentration of 3 to 40% by mass is maintained in a temperature range of 80 to 100 ° C. and then gradually cooled over 10 to 60 minutes. When the temperature is lowered to −10 to 30 ° C., an aldehyde and an acid catalyst are added, and an acetalization reaction is performed for 30 to 300 minutes while keeping the temperature constant. At that time, polyvinyl acetal having a certain degree of acetalization is deposited. Thereafter, the reaction solution is heated to a temperature of 30 to 80 ° C. over 30 to 300 minutes, and the temperature is maintained for 10 to 500 minutes. Next, a basic compound is added to the reaction solution, the acid catalyst is neutralized, washed with water, and dried to obtain polyvinyl acetal.

  The acid catalyst used in the acetalization reaction is not particularly limited, and any of organic acids such as acetic acid and p-toluenesulfonic acid or inorganic acids such as nitric acid, sulfuric acid and hydrochloric acid can be used. Preferably used.

  Although the aldehyde used for acetalization reaction is not specifically limited, It is preferable to acetalize with a C1-C8 aldehyde. Among them, it is preferable to use an aldehyde having 4 to 6 carbon atoms, and it is particularly preferable to use n-butyraldehyde. In the present invention, polyvinyl acetal obtained by using two or more aldehydes in combination can also be used.

で示される、Ａ層およびＢ層が含有する化合物（Ｉ）について説明する。Next, the general formula (I):

The compound (I) contained in the A layer and the B layer shown in FIG.

Wherein represents a hydrocarbon group of R ¹ and R ² 7-11 carbon atoms, which may be the same or different. As for carbon number of a hydrocarbon group, it is more preferable that it is 7-10, and it is more preferable that it is 7-9. If the carbon number is less than 7, the volatility of the compound (I) may be increased, which may be a problem. If the carbon number exceeds 11, the compatibility between the compound (I) and polyvinyl acetal may be reduced, or the compound ( The plasticizing effect of I) on polyvinyl acetal may be reduced.

The hydrocarbon group may be linear or branched, and may have an unsaturated bond. Moreover, some hydrogen atoms in the hydrocarbon group may be substituted with other atoms or substituents other than hydrogen atoms. Specific examples of R ¹ and R ² include alkyl groups such as heptyl group, octyl group, nonyl group, decanyl group, isodecanyl group and 3-heptyl group; alkenyl groups such as 3-hept-3-ene group; A chlorooctyl group etc. are mentioned. Among them, a hydrocarbon group having a branched structure is preferable in that it is difficult to undergo hydrolysis, and particularly when R ¹ and R ² are both 3-heptyl groups, compatibility with polyvinyl acetal and plasticization to polyvinyl acetal are preferable. It is particularly preferable from the viewpoint of effect.

R ¹ and R ² are preferably the same from the viewpoint of obtaining compound (I) at low cost. In the present invention, the compound (I) contained in the A layer and the compound (I) contained in the B layer may be the same or different, but are preferably the same from the viewpoint of availability. The compound (I) contained in the A layer and the B layer may be one kind alone or a mixture of two or more kinds.

  M represents a natural number of 3 to 10, preferably 3 to 8, and more preferably 3 to 4. Such a compound (I) has a low polarity and is preferable in that it is difficult to extract when the A layer and water contact. If m is less than 3, the volatility of the compound (I) may be increased, which may cause a problem. If m exceeds 10, the compatibility between the compound (I) and polyvinyl acetal may be reduced, or the compound (I) The plasticizing effect on polyvinyl acetal may decrease.

  Specific examples of the compound (I) include triethylene glycol di-2-ethylhexanoate, tetraethylene glycol di-2-ethylhexanoate, octaethylene glycol di-2-ethylhexanoate, triethylene glycol di-2-octanoate. And triethylene glycol didodecanoate. Among them, triethylene glycol di-2-ethylhexanoate is preferable because it is excellent in compatibility with polyvinyl acetal, has an excellent plasticizing effect on polyvinyl acetal, and is not easily hydrolyzed.

  The content a1 of the compound (I) in the A layer is 20 to 60 parts by mass, preferably 25 to 55 parts by mass, and more preferably 30 to 50 parts by mass with respect to 100 parts by mass of the polyvinyl acetal (A). It is. When a1 is less than 20 parts by mass with respect to 100 parts by mass of the polyvinyl acetal (A), sufficient sound insulation may not be exhibited when the obtained laminate is used for laminated glass. On the other hand, when a1 exceeds 60 parts by mass, sufficient mechanical strength may not be exhibited when the obtained laminate is used for laminated glass.

  The content b1 of the compound (I) in the B layer is 35 to 75 parts by mass, preferably 40 to 72 parts by mass, and more preferably 52 to 70 parts by mass with respect to 100 parts by mass of the polyvinyl acetal (B). is there. When b1 is less than 35 parts by mass with respect to 100 parts by mass of the polyvinyl acetal (B), sufficient sound insulation may not be exhibited when the obtained laminate is used for laminated glass. On the other hand, if b1 exceeds 70 parts by mass, the compatibility between the polyvinyl acetal (B) and the compound (I) in the B layer is lowered, and the transparency of the resulting laminate is impaired, or sufficient mechanical strength is obtained. It may not develop.

  In the present invention, (b1-a1)> 0, preferably 40> (b1-a1)> 7, more preferably 40> (b1-a1)> 15, and optimally 40 > (B1-a1)> 20. When (b1-a1)> 0, sufficient sound insulation is exhibited when the laminate is used for laminated glass. However, if (b1-a1) is 40 or more, the sound insulation may be insufficient.

で示される化合物（ＩＩ）について説明する。Next, the general formula (II) contained in the A layer and the B layer of the present invention:

The compound (II) represented by the formula will be described.

In the formula, R ³ is the same as either R ¹ or R ² , and n represents a natural number of 3 to 10. Compound (II) is similar to the chemical structure of Compound (I) and has excellent compatibility with Compound (I). Therefore, it is difficult to extract even when the laminate is in contact with water. It is also suitable for long-term use as an interlayer film. From the above viewpoint, it is particularly preferable that m of compound (I) and n of compound (II) are the same.

  Specific examples of the compound (II) include triethylene glycol mono 2-ethylhexanoate, tetraethylene glycol mono 2-ethyl hexanoate, octaethylene glycol mono 2-ethyl hexanoate, triethylene glycol mono 2-octanoate. And triethylene glycol monododecanoate. Among these, since the preferred compound (I) used in the present invention is triethylene glycol di-2-ethylhexanoate, it is preferable to use triethylene glycol mono-2-ethylhexanoate as the compound (II).

  The content a2 of the compound (II) in the A layer is preferably 0 to 2.5 parts by mass, more preferably 0.005 to 2.2 parts by mass with respect to 100 parts by mass of the polyvinyl acetal (A), and 0.035 to 2 parts by mass is more preferred. When a2 is within the above range, the adhesiveness between the laminate and the glass hardly changes even when the amount of moisture changes. Further, when the laminate is used as an interlayer film for laminated glass, the compound (II) is hardly extracted into water even if the laminate is in contact with water. Moreover, 0.01-3 mass parts is preferable, as for content b2 of compound (II) in B layer, 0.02-2.4 mass parts is more preferable, and 0.1-2.2 mass parts is further more preferable. When b1 is less than 0.01 parts by mass, sound insulation may be lowered when the moisture content of the laminate is changed. Further, when b1 is more than 3 parts by mass, for example, when the laminate is used for an interlayer film for laminated glass, when the laminate is in contact with water, a part of the compound (II) is extracted into water, and the appearance of the laminated glass The above disadvantages may occur.

  The compound (II) contained in the A layer and the compound (II) contained in the B layer may be the same or different, but are preferably the same from the viewpoint of availability. Further, the compound (II) contained in each of the A layer and the B layer may be a single type or a mixture of two or more types.

  In the laminated body of this invention, a2 / a1 is 0-0.05, Preferably it is 0.0007-0.045, More preferably, it is 0.001-0.04. When a2 / a1 is outside these numerical ranges, the sound insulation may be lowered when the moisture content of the laminate is changed when used as an interlayer film for laminated glass. b2 / b1 is 0.001 to 0.08, preferably 0.0015 to 0.07, and more preferably 0.002 to 0.06. When b2 / b1 is out of the above numerical range, when the moisture content of the laminate is changed and used as an interlayer film for laminated glass, the sound insulation may be lowered when the moisture content of the laminate is changed. .

  In the laminate of the present invention, a2 is 0 or (b2 / b1) / (a2 / a1)> 1.0. Preferably, when a2 is 0 or when a2 is not 0, (b2 / b1) / (a2 / a1)> 1.1. More preferably, when a2 is 0 or when a2 is not 0, [(b2 / b1) / (a2 / a1)]> 1.4. When a2 is not 0 and [(b2 / b1) / (a2 / a1)] is 1.0 or less, when the moisture content of the laminate is changed and used as an interlayer film for laminated glass, sound insulation May decrease.

  The laminate of the present invention may further contain an antioxidant, an ultraviolet absorber, an adhesion improver, and other additives.

  There is no limitation in particular in the kind of antioxidant which the laminated body of this invention may contain. For example, conventionally known phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like can be used. Of these, phenolic antioxidants are preferred. Antioxidants may be used alone or in combination of two or more. When the antioxidant is contained, the amount is not particularly limited, but is usually 0.0001 to 5% by mass, preferably 0.001 to 1% by mass with respect to the mass of the laminate. When the amount is less than 0.0001% by mass, a sufficient effect as an antioxidant may not be obtained, and when the amount is more than 5% by mass, a remarkable effect cannot be expected.

  There is no limitation in particular in the kind of ultraviolet absorber which the laminated body of this invention may contain. For example, conventionally known benzotriazole ultraviolet absorbers, oxalic anilide ultraviolet absorbers, benzoate ultraviolet absorbers, and the like can be used. The ultraviolet absorbers may be used alone or in combination of two or more. When the ultraviolet absorber is contained, the amount thereof is not particularly limited, but is usually 0.0001 to 5% by mass, preferably 0.001 to 1% by mass with respect to the mass of the laminate. If the amount is less than 0.0001% by mass, a sufficient effect as an ultraviolet absorber may not be obtained.

  The laminate of the present invention is particularly preferably used as an interlayer film for laminated glass. In that case, it is preferable that an adhesion adjusting agent is added to the layer that adheres to the glass. Examples of the adhesion adjusting agent include sodium salt, potassium salt, magnesium salt and the like of organic acids such as acetic acid, propionic acid, butanoic acid, hexanoic acid, 2-ethylbutanoic acid and 2-ethylhexanoic acid. More than one kind may be added. In particular, when the layer that adheres to the glass is the A layer, from the viewpoint of obtaining a laminate in which the adhesiveness does not change even when the moisture content changes, magnesium acetate, magnesium acetate tetrahydrate, magnesium butanoate, Magnesium salts such as magnesium 2-ethylbutanoate and magnesium 2-ethylhexanoate are preferably added, and magnesium acetate tetrahydrate is preferably added to the A layer.

  The addition amount of the adhesion adjusting agent is 0.001 to 0.1 parts by mass with respect to 100 parts by mass of the polyvinyl acetal (A) from the viewpoint of penetration resistance of the laminated glass and prevention of glass piece scattering when the laminated glass is broken. Is preferable, 0.005-0.08 mass part is more preferable, 0.01-0.06 mass part is further more preferable, 0.03-0.055 mass part is especially preferable.

  The method for producing the laminate of the present invention is not particularly limited, and conventionally known methods can be applied. For example, the component constituting the A layer and the component constituting the B layer are each melt-kneaded with an extruder and subsequently co-extruded with a multilayer film forming machine; the A layer and the B prepared individually by hot pressing or casting after the melt-kneading The method of laminating | stacking by laminating | stacking a layer and sticking by hot press etc. as needed is mentioned.

  When the laminate of the present invention is used as an interlayer film for laminated glass, it exhibits a certain characteristic with a wide range of moisture content. Therefore, the moisture content of the interlayer film for laminated glass that is temporarily bonded by an autoclave after temporary bonding with a nip roll is reduced. Laminated glass can be produced by a method in which the moisture content of the laminated glass interlayer film that is heat-treated under reduced pressure using a vacuum bag or a vacuum laminator is adjusted to a relatively low level. The moisture content of the laminate of the present invention is preferably 0.01 to 1.0% by mass, more preferably 0.02 to 0.9% by mass, and further preferably 0.03 to 0.8% by mass. The moisture content of the laminate of the present invention is less than 0.01% by mass because it takes a long time to adjust to such a moisture content, and the moisture content of the laminate of the present invention is not preferred. When the amount exceeds 1.0% by mass, the adhesion of the laminate to the glass and the transparency may change, which is not preferable.

  There is no limitation in particular in the thickness of A layer and B layer in the laminated body of this invention. The thickness of the A layer is usually preferably 0.05 to 1.2 mm, more preferably 0.07 to 1 mm, further preferably 0.1 to 0.6 mm, and particularly preferably 0.12 to 0.5 mm. If the thickness is less than 0.05 mm, the mechanical strength of the laminate of the present invention tends to decrease, and for example, it may be insufficient for use as a laminated glass interlayer. When it is thicker than 1.2 mm, the laminate of the present invention tends to have insufficient flexibility. For example, in use as a laminated glass interlayer, the safety of the resulting laminated glass may be lowered.

  The thickness of the B layer is usually preferably 0.01 to 1 mm, more preferably 0.02 to 0.6 mm, and still more preferably 0.05 to 0.4 mm. If the thickness is less than 0.01 mm, the sound insulation performance of the laminated glass using the laminate of the present invention as an intermediate film may deteriorate, and even if it is thicker than 1 mm, the mechanical strength and sound insulation performance of the laminate of the present invention are more than that. There is a tendency not to improve.

  When the laminate of the present invention is used as an interlayer film for laminated glass, the laminate is composed of three or more layers, and the outermost layers are both A layers. It is preferable from the viewpoint of adjustment. Examples of the laminate in which the outermost layers are both A layers include A layer / B layer / A layer, A layer / B layer / A layer / B layer / A layer, and the like. When two or more A layers are included, the thickness of each layer may be the same or different. When two or more B layers are included, the thickness of each layer may be the same or different. .

  When the laminate of the present invention is used as an interlayer film for laminated glass, the thickness of the laminate is not particularly limited, but usually 0.2 to 2 mm is preferable, 0.25 to 1.8 mm is more preferable, and 3-1.5 mm is more preferable. If the thickness of the laminate is thinner than 0.2 mm, the mechanical strength tends to be insufficient, and if it is thicker than 2 mm, the flexibility tends to be insufficient.

  The glass material when using the laminate of the present invention as an interlayer film for laminated glass is not particularly limited, inorganic glass such as float plate glass, heat tempered glass, chemically tempered glass; organic glass such as polymethyl methacrylate, polycarbonate, etc. Conventionally known glass can be used. These may be colorless or colored, transparent or non-transparent, and two or more of them may be used in combination. Although there is no limitation in particular in the thickness of glass, Usually, 20 mm or less is preferable and 10 mm or less is more preferable.

  When using the laminated body of the present invention as an interlayer film for laminated glass, the shape of the outermost surface of the laminated body is not particularly limited, but considering the handleability when producing a laminated glass (for example, bubble removal in the laminate), It is preferable to form a concavo-convex structure on the outermost surface of the laminate by a conventionally known method such as melt fracture or embossing.

  The method of producing laminated glass using the laminate of the present invention as an interlayer film for laminated glass is not particularly limited. For example, a method of undergoing a decompression step using a vacuum laminator device or a vacuum bag; A conventionally well-known method is mentioned, such as the method of not passing through the pressure reduction process to process.

An example of the production conditions when using a vacuum laminator apparatus is 10 to 300 minutes at a temperature of 100 to 200 ° C., preferably 130 to 160 ° C. under a reduced pressure of 1 × 10 ^{−6 to} 3 × 10 ⁻² MPa. Then, an interlayer film for laminated glass is laminated with glass. When using a vacuum bag, it laminates by processing for 10 to 300 minutes at 130-145 degreeC under the pressure of ² * 10 ^{< -4} > ^-3 * 10 ^<-2 > MPa, for example. When producing laminated glass by the method of passing through these decompression steps, it is necessary to use a laminate having a moisture content of 0.01 to 0.3% by mass, and bubbles are generated in the laminate during lamination. From the viewpoint of preventing this, it is preferable.

  An example of the operating conditions of the nip roll in the method of processing with an autoclave after temporarily bonding with the nip roll is that the glass and the laminate are heated to 50 to 120 ° C. with an infrared heater or the like, and then pressure bonded with the roll and temporarily bonded. The process of autoclaving is performed at a temperature of 130 to 145 ° C. for 30 to 200 minutes, for example, under a pressure of 1.0 to 1.5 MPa. When producing laminated glass by a method that does not go through such a decompression step, the moisture content of the laminate is 0.4 to 0.7% by mass from the viewpoint of simplifying the humidity control (drying) step of the laminate. It is preferable to use one made to a degree.

  EXAMPLES Hereinafter, although an Example etc. demonstrate this invention further in detail, this invention is not limited at all by these Examples.

(Preparation of PVB-1)
In a 5 L (liter) glass container equipped with a reflux condenser, thermometer, and squid type stirring blade, ion-exchanged water 4050 g, polyvinyl alcohol (PVA-1) (viscosity average polymerization degree 1700, saponification degree 99 mol%) 330 g (PVA concentration 7.5%), and the contents were heated to 95 ° C. and completely dissolved. Next, after gradually cooling to 5 ° C. over about 30 minutes with stirring at 120 rpm, 188 g of butyraldehyde and 140 g of 35% hydrochloric acid were added, and a butyralization reaction was performed for 30 minutes. Thereafter, the temperature was raised to 60 ° C. over 60 minutes, held at 60 ° C. for 120 minutes, and then cooled to room temperature. After washing the polyvinyl acetal resin with ion-exchanged water, the remaining hydrochloric acid was neutralized with an aqueous sodium hydroxide solution, further washed with ion-exchanged water, dehydrated and dried to obtain polyvinyl butyral (PVB-1). The properties of the obtained PVB-1 were measured according to JIS K6728. As shown in Table 1, the average degree of acetalization was 68 mol%, the average residual vinyl ester group amount was 1 mol%, and the average residual hydroxyl group amount was 31 mol. %Met.

(Preparation of PVB-2)
In the preparation of PVB-1, the reaction was carried out in the same manner except that the amount of butyraldehyde used was changed to 194 g to obtain PVB-2. The properties of the obtained PVB-2 were measured according to JIS K6728. As shown in Table 1, the average degree of acetalization was 71 mol%, the average amount of residual vinyl ester groups was 1 mol%, and the average amount of residual hydroxyl groups was 28 mol. %Met.

(Preparation of PVB-3)
In the preparation of PVB-1, after changing PVA-1 to 330 g PVA-2 (viscosity average polymerization degree 1700, saponification 92 mol%) and butyraldehyde use amount to 198 g, and further carrying out a butyralization reaction at 5 ° C. The temperature was raised to 67 ° C over 70 minutes, and PVB-3 was obtained in the same manner except that the reaction was carried out at 67 ° C for 120 minutes. When the specified PVB-3 was measured according to JIS K6728, as shown in Table 1, the average degree of acetalization was 74 mol%, the average residual vinyl ester group amount was 7 mol%, and the average residual hydroxyl group amount was 19 mol. %Met.

(Preparation of PVB-4)
In the preparation of PVB-3, after changing PVA-2 to 330 g of PVA-3 (viscosity average polymerization degree 1700, saponification 90 mol%) and butyraldehyde use amount to 204 g, and further carrying out a butyralization reaction at 5 ° C. The temperature was raised to 67 ° C. over 70 minutes, and PVB-4 was obtained in the same manner except that the reaction was carried out at 67 ° C. for 120 minutes. The properties of the obtained PVB-4 were measured according to JIS K6728. As shown in Table 1, the average degree of acetalization was 75 mol%, the average residual vinyl ester group amount was 9 mol%, and the average residual hydroxyl group amount was 16 mol. %Met.

Example 1
(Production of laminate)
100 parts by weight of PVB-1, 36 parts by weight of triethylene glycol di-2-ethylhexanoate as compound (I), 0.3 parts by weight of triethylene glycol mono-2-ethylhexanoate as compound (II) and 0.048 parts by mass of magnesium acetate tetrahydrate was kneaded in a Laboplast mill at 160 ° C. for 8 minutes. The obtained kneaded material was pressed for 30 minutes in a mold having a thickness of 0.38 mm under the conditions of 160 ° C. and 50 kg / cm ² to obtain a sheet A having a thickness of 0.38 mm.
On the other hand, 100 parts by mass of PVB-3, 58 parts by mass of triethylene glycol di-2-ethylhexanoate as compound (I) and 1 part by mass of triethylene glycol mono-2-ethylhexanoate as compound (II) It knead | mixed for 160 minutes at 160 degreeC with the Laboplast mill. The obtained kneaded material was pressed for 30 minutes in a 0.15 mm thick mold at 160 ° C. and 50 kg / cm ² to obtain a sheet B having a thickness of 0.15 mm. Sheet A and sheet B are stacked in the order of sheet A / sheet B / sheet A, and pressed in a 0.91 mm thick formwork at 135 ° C. and 10 kg / cm ² , and layer A (0.38 mm) / Laminated body-1 consisting of B layer (0.15 mm) / A layer (0.38 mm) was obtained.

(Production of low moisture content laminated glass using a vacuum bag)
The laminate-1 of 30 cm × 30 cm was stored in a desiccator adjusted to 23 ° C. and 5 to 10% RH for 5 days to adjust the humidity (dry). The layered product-1 after humidity control is quickly sandwiched between two float glasses (30 cm x 30 cm x 2.2 mm), placed in a vacuum bag, and the inside of the vacuum bag is decompressed to 3 x 10 ^-3 MPa at room temperature. While maintaining the degree of decompression, the mixture was heated to 135 ° C. over 30 minutes and held at 135 ° C. for 2 hours to obtain laminated glass-1 (V). The moisture content of laminate-1 in the obtained laminated glass-1 (V) was 0.11%. In addition, the moisture content hits the part which is separated from 1 cm from the edge part of laminated glass-1 (V) with a hammer, breaks glass, takes out laminated body-1 rapidly, and the said sample 0.5g is Mitsubishi Corporation. Using a Karl Fischer moisture meter (KF-200 (capacitance method moisture meter) and VA-200 (moisture vaporizer) in combination) manufactured by Chemical Analytic, heated at 200 ° C. for 10 minutes, Measured by quantification.

(Preparation of high moisture content laminated glass that is temporarily bonded with a nip roll and then fully bonded with an autoclave)
The sheet-1 of 30 cm × 30 cm was stored for 5 days in an atmosphere of 23 ° C. and 28% RH to adjust the humidity. The layered product-1 after humidity control was quickly sandwiched between two float glasses (30 cm × 30 cm × 2.2 mm), heated to 80 ° C., and temporarily bonded using a nip roll. The obtained temporary adhesive body was put into an autoclave and treated for 60 minutes under conditions of 135 ° C. and 1.2 MPa to obtain laminated glass-1 (NA). The moisture content of laminated body-1 in the obtained laminated glass-1 (NA) was 0.52%. In addition, the moisture content was calculated | required by the method similar to laminated glass-1 (V).

(Sound insulation measurement)
Laminated glass-1 (V) and laminated glass-1 (NA) were each cut into a size of 2.5 cm × 30 cm, and were shaken under a 25 ° C. atmosphere (EMIC Corporation, small vibration generator 512-A). The frequency response function at that time is detected with an FFT analyzer (DS-2100, manufactured by Ono Sokki Co., Ltd.), and at 3000 Hz using servo analysis software (DS-0242, manufactured by Ono Sokki Co., Ltd.). The loss factor was calculated. The larger the loss factor, the better the sound insulation performance of the laminated glass.

(Penetration resistance evaluation)
The 30 cm × 30 cm laminated glass-1 (V) and laminated glass-1 (NA) obtained above were conditioned at 23 ° C. for 24 hours. An iron ball (hard sphere) having a mass of 2260 g and a diameter of 82 mm was dropped from a height of 6 m onto the central portion of the laminated glass. The same evaluation was performed for four laminated glasses, and for three or more laminated glasses, A was the case where the hard sphere did not penetrate within 5 seconds after the hard sphere collided. The case where the hard sphere did not penetrate within 5 seconds after the collision occurred was designated as B, and the other cases were designated as C.

(Laminated glass cooling test)
Laminated glass-1 (V) and laminated glass-1 (NA) were held at 80 ° C. for 2 hours, then cooled from 80 ° C. to −20 ° C. over 50 minutes, and further held at −20 ° C. for 2 hours. The mixture was heated from −20 ° C. to 80 ° C. over 50 minutes (this treatment is defined as one cycle). After repeating this cycle a total of 30 times, check if there is no separation between the glass and the laminate, and between the A layer and the B layer in the laminate. What was only in the part of 0-1 cm was set to B, and what was peeled in the part exceeding 1 cm from the glass edge part was set to C.

(Laminated glass hot water treatment test)
Laminated glass-1 (NA) was immersed in warm water of 60 ° C. for 12 hours, and then allowed to stand for 108 hours in an atmosphere of 23 ° C. and 28% RH (this treatment is defined as one cycle). After repeating this process 10 times, at the end of each laminated glass, the presence or absence of occurrence of defects (peeling of glass and interlayer film for laminated glass, peeling of interlayer of interlayer film) due to extraction of components contained in the laminate is visually observed. confirmed.

(Examples 2-33, Comparative Examples 1-9)
A laminate and a laminated glass were produced in the same manner as in Example 1 except that the compositions of the A layer and the B layer were changed as shown in Table 2 and Table 4. The obtained laminated glass was evaluated in the same manner as in Example 1. The results are shown in Table 3 and Table 5.

When the laminate of the present invention is used as an interlayer film for laminated glass, it is produced with a low moisture content by a vacuum laminator or a vacuum bag, or is produced with a high moisture content by an autoclave after temporary bonding with a nip roll. Can exhibit the same excellent characteristics.

  In the laminate of the present invention, the plasticizer contained in the laminate is difficult to be extracted by water and is not easily volatilized. When used as an interlayer film for laminated glass, even if the moisture content is changed, a change in sound insulation properties does not occur. Absent.

Claims (7)

General formula (I): 100 parts by mass of polyvinyl acetal (A) having an average residual hydroxyl group content of 25 to 45 mol%:

(Wherein R ¹ and R ² represent the same or different hydrocarbon groups having 7 to 11 carbon atoms, and m represents a natural number of 3 to 10). Content of Compound (I) a1 is 20 to 60 parts by mass, and the general formula (II):

(Wherein R ³ is the same as either R ¹ or R ² , n represents a natural number of 3 to 10) and the A layer has an a2 mass part content of compound (II); The content b1 of the compound (I) is 35 to 75 parts by mass with respect to 100 parts by mass of the polyvinyl acetal (B) having an average residual hydroxyl group content of 10 to 35 mol%, and the content of the compound (II) is b2 parts by mass. A2 is 0 or (b2 / b1) / (a2 / a1)> 1, (b1-a1)> 0, and a2 / a1 is 0 to 0.00. 05, and b2 / b1 is 0.001 to 0.08. The laminate according to claim 1, wherein the A layer contains 0.001 to 0.1 parts by mass of a magnesium salt with respect to 100 parts by mass of the polyvinyl acetal (A). The laminate according to claim 1 or 2, wherein m and n are the same. R ¹ and ^{R 2} are the same, the laminated body according to any one of claims 1 to 3. R ¹ and ^{R 2} is 3-heptyl, laminate according to any one of claims 1 to 4. The laminate according to any one of claims 1 to 5, wherein the laminate is composed of three or more layers, and both outermost layers are A layers. Laminated glass containing the laminate according to any one of claims 1 to 6.